Hydroformed solvent composition



Patented Sept. 13, 1938 UNITED STATES "PATENT OFFICE Robert T. Haslam, Westfield, N. J., assignor to Standard-I. G. Company, a corporation of Delaware No Drawing. Application August 28, 1936, Serial No. 98,341

21 Claims.

The present invention relates to improved solvents and solvent compositions and more specifically comprises a synthetic hydroformed solvent derived from petroleum and liquid distillation or extraction products thereof and also comprises new coating compositions in which the improved solvent vehicle is incorporated. This application is a continuation of my prior applications Serial No. 583,703, filed December 29, 1931 and Serial No. 640,670, filed November 1, 1932, and relates especially to coating compositions containing the improved solvents. My invention will be fully understood from the following description of the method of manufacture and use of the improved solvents.

It is known that hydrocarbon oil distillates, such as those obtainable from petroleum, may be hydroformed by destructive hydrogenation at elevated temperatures an pressures to produce products essentially different from those produced by simple hydrogenation or even by destructive hydrogenation at lower temperatures. For :example, the hydro'jormed products when used .as motor fuels possess antiknockingchar- 'acteristics to a much greater degree than shown by the original oils or by products of other types of hydrogenation. These hydroformed products are produced from hydrocarbon oil distillates such as burning oil and gas oil and ingeneral til 30 :from hydrocarbon oils of a boiling range in'cluding that of gasoline and extending up to about 650 to 700 Fxor somewhat higher. These-distillateoils are passed in vapor phase with free hydrogen over suitable catalysts'at a'pressurein I 3;, excessof-ZO atmospheres and preferably 50*to 200 atmospheres .or higher-and at a temperature above about 900;F.- andpreferably within the range of-1 about 930 to '-l050F. with a suitable partial pressure of hydrogen and time of contact to secure a destructive hydrogenation without the formationof appreciable amounts of polymerized or coky material. "The hydrogen supplied is {preferably within the range of about 1,000 to I ',4,000-cubic feet per barrel-of feed oil, the amount generally depending upon the gravity and boiling range of the charging stock. A greater proportion of hydrogen may be used with suitable variation in feed rate, temperature and pressure as is known in the art. The feed rate depends upon the reaction temperature, and other operating conditions such as the partial pressure of hydrogen and may be suitably about 1.5 to 4 volumes of oil per volume of catalyst filled reaction space per hour. The catalysts preferably comprise the oxides or sulfides of the metals of the VI group of elements with suitable promoters of the alkaline earth or earth oxides. Such catalysts-are insensitive to sulfur poisoning and are suitably classified as sulfactive.

The product of such a destructive hydrogenation process possesses highly desirable solvent X properties throughout its boiling range. Fractions of desired volatility of these hydroformed distillates may. be generally used in vehicles for resins, varnish gums, drying oils and nitrocellulose in varnish lacquerand paint iormulae wherever aromatic Jhydrocarbon solvents such as benzene, toluene, xylene, turpentine oils and high flash coal tar'naphthas and the like are suitable, and may be substituted, either partially or en tirely for' such hydrocarbons. Other solvents, made by other processes, if substantially identical with the solvents made by the-'hydroforming process, may also be used in the present inven-. tion.

Fractions suitable for use in this invention inclu-de'both the lowboilingrelatively volatile fractions which evaporate readily from surfaces un- .der atmospheric conditions and the diflicultly volatile fractions :which evaporate more slowly and are used for applications where temperatures above atmosphericare available for the drying or setting oft-he compositions. The still higher boiling fractions in the des'tructively 'hy-' drogenated product may be recycled in the hydrogenation process and converted into. the-lower boiling-solvent fractions.

'-.'The lower limit forthe boiling range of the hydroformed solvents for most commercial purposes is fixed preferably at about'122 E, as fractions boiling below this point are so volatile as to constitute explosion hazards during application of the lacquers, etc. in which they are used. The lower boiling fractions may also cause the lacquer to show brush marks or moisture blush and hence, although their solvent power is excellent, these fractions should be used either in small amounts or with considerable precautions.

As the relatively volatile fractions are used primarily in surface coating compositions such as lacquers, varnishes, paints and the like, from which the solvent should readily evaporate, higher boiling fractions which cause a greasy or very slow drying coat are preferably eliminated.

The fractions of relatively low volatility include those boiling above about 280 to 300 F. and up to about 550 to 600 F. and having a flash point above about 80 to 100 F. These fractions represent improved high flash solvents which may be used in substitution for high flash coal tar naphthas, turpentine, xylol, dipentene and the like, in preparing surface coating compositions. Examples of such coating compositions are enamels, varnishes, lacquers, paints and the like. The high flash hydroformed solvents are especially suitable for use in coating compositions for force. or bake drying or for applications in exposure to direct sunlight.

The solvent power of the hydroformed solvents depends not only'upon the operating conditions used in the destructive hydrogenation process but also to some extent upon the source of the hydrocarbon oils used as feed stocks. Operating conditions in the destructive hydrogenation process being equal, hydroformed solvents produced from California crudes possess higher solvent power for oxygenated hydrocarbons, such as py-' roxylin or kauri gum, than corresponding solvents from Mid-Continent crudes, while solvents from naphthenic base crudes possess even higher solvent power. Cracked cycle gas oils, especially such oils from asphaltic or naphthenic base crudes, form desirable feed stocks. Extraction products such as those produced in refining oils with solvents having a selective solvent action for non-paraffinic hydrocarbons, such as phenol or liquid sulfur dioxide, are preferred feed stocks for the production of these solvents by destructive hydrogenation, and hydroformed solvents superior even to pure aromatic hydrocarbons such as toluene and xylene and to coal tar naphthas may thereby be produced. Hydroformed solvents prepared by destructive vapor phase hydrogenation under the operating conditions defined above, are far superior to the corresponding straight run or cracked naphthas from the same crudes. In addition to possessing superior solvent power, the hydroformed naphthas are hydrunsulfed during the destructive hydrogenation process and the sulfur content of even high sulfur oils is reduced below that at which bad eflects on lead pigments and the like are noticed.

The following examples are illustrative of one method of preparing hydroformed solvents and of a few uses towhich these improved solvents may be put, but my invention is not to be limited thereto.

Example 1.-Cracked cycle stock from a California crude is destructively hydrogenated over a sulfactive catalyst at a pressure of 3,000 pounds per square inch and an average catalyst temperature of 950 F. A fraction of the product having an end point of 392 F. is removed from the process and the higher boiling fractions are continuously recycled. The ratio of hydrogen to oil in the feed to the system is 2,200 cubic feet of hydrogen per 42 gallon barrel of oil. The specifications of the feed stock are as follows:

Gravity, A. P. I 25.9

I. B. P., F 342 5 Percent at 374 F 3.0 Percent at 400F 9.0 Percent at 420 F 16.5 Percent at 460 F 31.0 Percent at 500 F 68.0 m Percent at 550 F 91.0 Percent at 600 F 97.0

F. B. P., F 602 Sulfur percent" 0.554 Aniline point "F i '79 15 The specifications of the product are:

Gravity, A. P. I ,7 43.4

I. B. P., F 140 Percent at 158 F 2.0 -Percent at 212 F 19.5 Percent at 284 F 56.0 Percent at 356 F 69.5 Percent at 374 F 95.0

F. B. P., F 392 25 Refractive index at 20 C 1.4625 Sulfur "percent" 0.025 Gum (porcelain dish) mgs 3.0 Color +25 Doctor and corrosion Passes Aniline point F -1 39 Dimethyl sulfate value percent.. 31.5 Kauri-butanol value 57 The dlmethyl sulfate absorption test is made by shaking 10 cc. of dimethyl sulfate with 10 cc. of the vehicle. The increase in volume of the dimethyl sulfate layer is expressed in per cent of the original volume of'the vehicle. The dimethyl sulfate absorption value for hydrocarbon 40 distillate vehicles prepared from petroleum by distillation, cracking or liquid phase hydrogenation varies between about 4 and 10%.

The kauri-butanol value is determined according to the method given in. Gardner's Physical and Chemical Examination of Paints, varnishes and Colors. This value is the number of cos. of the vehicle that produces a definite cloud point when added at 77 F. to 20 grams of a standard solution prepared by dissolving 100 grams of kauri gum in 500 grams of pure butanol. This value for petroleum: oils not treated by the destructive hydrogenation process usually ranges from about 25 to 40.

A lacquer of the following composition is prepared using the above hydroformed solvent. The parts are by weight:

Parts Nitrocellulose (V sec.) 15 Ethyl alcohol 40 0 Hydroformed solvent 40 Butyl acetate 4 80 Butyl alr-nhnl 20 Ethyl acetate--- 9 Castor Oil 1 5 The above formula gives a good lacquer with highly desirable drying and film characteristics.

This lacquer compares favorably with a corre- A considerably greater amount of hydroformed I 1. Fraction boiling below 167 F. 2. Fraction boiling between 167 F. and 239 F. 3. Fraction boiling above 239F.

Lacquers corresponding to the above formula are prepared with each of these fractions and are all satisfactory. No blushing takes place on application and drying of the lacquer even when using the lowest boiling fraction.

Example 2.A cracked hydrocarbon distillate from a Mid-Continent crude is destructively hydrogenated under substantially the same conditions as those described in Example 1. The feed stock has a gravity of 37.8 A. P. I. and boils between 435 and 629 F. It contains 0.179% sulfur and has an aniline point of 159 F. The product has the following specification:

Gravity, A. P. I 54.9 I. B. P., F 118' Percent at 158 F 7.0 Percent at 212 F 33.5 Percent at 284 F 68 Percent at 356 F 93 Percent at 374 F v 97 F. B. P., F 388 Refractive index at 20 C 1.4310 Sulfur percent.. 0.020 Gum (porcelain dish) mgs 2.5 Color +27 Doctor and corrosion Passes Aniline point, 91 Kauri-butanol value 41.7 Dimethyl sulfate value percent 16.5

This hydroformed solvent when used in the lacquer formula given in Example 1 also gives a good lacquer comparing favorably in all characteristics with the same lacquers made with benzene or the California hydroformed solvent.

Example 3.-A lacquer of the following comof the coal tar hydrocarbons. The hydroformed solvents also have none ,of the irritating and smarting effects on the eyes which have made coal tar hydrocarbons so objectionable.

Example 4.An especially suitable lacquer solvent may be prepared by destructively hydrogenating the oil fraction obtained by extracting burning oils with liquid sulfur dioxide. A hydroformed product obtained by this method has the following specifications:

Gravity, A P. I 19.7 I. B. P., F 150 F. B. P., "F v 522 Dimethyl sulfate value percent 1 100 Kauri-butanol value 117.3

Hydroformed solvents of suitable boiling range may be readily prepared from this product by distillation, and possess greatly improved solvent properties over the hydroformed solvents already described, as indicated by the dimethyl sulfate and kauri-butanol values. Hydroformed solvents with kauri-butanol values even above Y may be prepared by this method.

Example 5.-A varnish of the following composition is prepared using the hydroformed solvent described in Example 1. The parts are by weight:

. Parts Kauri gum 80 Rosi 20 Linseed oil 116 Tung oil (raw) 40 Lime- 2 Lead oxide 2.5 Manganese acetate n 0.5 Hydroformed solvent 200 kauri-butanol numbers, increases with increase in boiling point for the hydroformed solvents, while it decreases for the coal tar naphthas.

position is prepared using the hydroformed solm h Boning vent of either Example 1 or Example 2, above. Solvent Ji a tan l The parts are by weight: numb" Parts Nitrocellulose (/2 sec., wet with 30% denaggggfggggggggg: g: ":1 9 g fig: g g tured alcohol) gygriorn1 edsclvent#3.,-.. 200 419-550 88:0 Ester o (lu a i ii fiez i l toluol 266-358 94,0 Hydroformed solvent 44 Commercial xyloL 268-285 82.7 Dibutyl phthalate 5 .';.?Rfi??:::::::: "'"a' 2&3; it Butyl alcohol 8 Petroleum naphtha--- 311-413 29.8 Ethyl 32 33233 iff??ffi.?i:.'if?:::::: 1% 23332 33 Butyl acetate- 16 These lacquers are also satisfactory in all respects as compared with the same lacquers made with aromatic hydrocarbon solvents.

The toxicity of the above compositions is greatly decreased by. the substitution of hydroformed solvents, which are substantially non-toxic, for the coal tar aromatic hydrocarbon solvents which are known to have toxic properties.

The odor of the hydroformed solvents is quite different from and much more pleasant than that There is no commercially available hydrocarbon solvent boiling above 420 F. with solvent properties even approaching those of the'Hydroformed Solvent #3 of the above table. The hydroformed solvents boiling above about 420 F. and having kauri-butanol values above 60 to 80, accordingly representan entirely new series of solvent products, the exact chemical compositions of which are unknown except in that they are composed of liquid hydrocarbons.

Example 6.-A petroleum kerosene or "waterwhite" fraction is extracted with liquid sulfur dioxide and the fraction of the extract boiling between 31 1 and 592 F. is used as feed stock for a destructive hydrogenation process. This extract fraction has a gravity of 31.7 A. P. 1., an aniline sensibility point of 32 F. and a sulfur content of 0.640%. It is destructively hydrogenated over a sulfactive catalyst at a pressure of 3,000 pounds per square inch and an average catalyst temperature of 979 F. The product is treated with sulfuric acid, neutralized with caustic soda, washed with water, and then separated into the following fractions by distillation.

Fraction 1 2 3 Gravity, "A. P. I 33. 7 27. 5 17. 7 Aniline point, F v 19 22 42 Kauri-butanol number. 74 78 88 Initial, F 276 359 421 5% oil, "F 300 370 436 60% oil, F 326 385 464 011, "F 378 426 543 Fi 398 468 582 Solubility of blown castor oil Solvent Solubility Tolerance Petroleum naphtha thinner Insoluble 0 High flash coal tar naphtha Soluble 4 Hydrolormed solvent A. .Do 7 Hydrolormed solvent B. Do 9 Hydroformed solvent 0. Do. 12 Hydroiormed solvent D.. 23

The hydroformed solvents may also be used in lacquer preparations in admixture with lacquer vehicles generally, such as those containing aliphatic alcohols, ketones, and fatty acid esters and are especially desirable when used with secondary amyl, secondary butyl and isopropyl alcohols and their acetic esters. Pyroxylin and the other cellulose derivatives, plasticizers, gums Resin-Relative solubility in solvent Boiling Solvent range, Damm.

F. Bats; Rezyl Rezyl Rezyl Rezyl Teglac Amberol Amberol Amberol ME #12 #14 #19 #1102 #15 F-7 K-12-A 801 Hydroiormed solvents:

Hyd. solv. A 200-275 4 70 28 So]. 260 220 Hyd. solv. B 275-365 So]. 200 4 98 50 Sol. 801. Sol. Sol. Hyd. solv. C 365-419 Sol. 4 98 50 S01. Sol. Sol. Sol. Hyd. solv. D 419-550 Sol. 300 30 132 60 Sol. 801. Sol. Sol. Pet. naphtha 311-413 42 28 2 20 13 39 23 78 31 Coal tar solvents:

Benz Sol. Sol. 28 S01. S01. S01. Sol. S01. S01, Toluol S01. S01. 6 S01. S01. S01. Sol. S01. So]. High fish naptha. 302-400 Sol? 150 2 90 48 Sol. Sol. 320 150 (Base solvent for resin). T T TA T T A 'I A T It is apparent from the above table that the hydroformed solvents are much better solvents for these resins than are the ordinary petroleum naphthas. The fractions of the hydroformed solvents boiling within and above the range of high flash coal tar naphtha are better resin solvents than this coal tar distillate solvent.

The relative solubility in the above table is expressed as the number of cubic centimeters of the solvent that can be added to 20 grams of a resin solution, containing 5 parts by weight of a base solvent to one part of resin, before a turbid solution results. The base solvent was butyl alcohol (A) in all cases except that toluol (T) or a mixture of toluol and butyl alcohol (TA) were used when butyl alcohol failed to dissolve the resin.

Certain of these resins are soluble in the hydroformed solvents alone. For example, 5 parts by weight of each of the hydroformed solvents A, B, C and D gives a clear solution with one part of the Teglac 15 or the Amberol F-7 resins. These same resins give a. turbid solution or suspension in ordinary petroleum naphtha solutions containing 100 parts of naphtha and only part of the resin. These resins are insoluble in the petroand resins, such as the synthetic and modified phthalic glycerides and phenol formaldehyde resins, dammar gums and others commonly known to the lacquer industry may be used with these vehicles in making lacquer compositions. For example, a satisfactory lacquer may be prepared with cellulose ether and a hydroformed solvent as the only constituent of the vehicle. The hydroformed solvents may also be used in homogeneous vehicles containing drying oils suitable for use alone and for admixture with pigments for the preparation of paints and enamels.

These new synthetic petroleum distillates therefore provide highly desirable petroleum vehicles of high solvent power for free use in coating compositions of very wide and diverse character.

The hydroformed solvents have been separarated by distillation into a great number of fractions of very narrow boiling range and it has been i [this solvent may hydroi'ormed solvent and is not.--restrictcd to the "boiling; rangescor-rc'sponding'tozbenzene, toluene or xylene indicates that thescnew, solvents-do; the presence 01. these aromatic not depend upon compounds} for their improved solvent cha'rac,v

This invention antes. available a new type or solvent for preparing "surface coating synthetic .compositionsand the like,' and has the added advantage over coalrtarjsolventsl andpine oils that readily prepared in substan i tiallyunlimitedquantity and at a much cheaper cost than that ofYcompetlngpsolverits even -approaching it insolvent powen, r

My invention is not to be limited to any illus trative examples nor to any theory regarding the, solvent Jcharacteristicsjof the hydroformed produjctbut only to the following claims in which a solvent prepared by'destructive' hydrogenation h oif a petroleum distillate in vapor, phase at a tem- I wish to'clairn all novelty as ifar asthc prior art permits. V I claim: F f

A coating mpositioncontaining film-fo m.-

ing ingredients dissolved in a vehicle comprising perature' above about 900 Faand a pressure in excess of 20 atmospheres.

2. As a coating composition, a composition comprising non-volatile coating substances which are soluble in organic solvents incorporated in an organic vehicle comprising a hydroformed syn,- thetic solvent prepared from a petroleum distillate by destructive hydrogenation in vapor phase at a temperature above about 900 F. and a pressure in excess of 20 atmospheres. v H v 3. A coating composition comprising film-forming ingredients dissolved in a vehicle comprising a volatile hydrocarbon liquid, having a kauributanol value above 40, and prepared by destrucoilwith liquid sulfur 6. Composition according to-claim. 3, in which tive hydrogenation of a petroleum distillate in vapor phase at a temperature above about 900 F. and a pressure in excess of 20 atmospheres. 4. Compositionaccordingto claim 3, in which said petroleum distillate. is,a.-non-.parafllnic conicentrate; derived tfroma petroleum :oilby treatment with a solvent having a selective action between paraffinic and non-parafiinic components thereof.

5. Compo'sitionaccording to claim 3, in which' 1 said petroleum distillate is a non-paraflinic concentrate secured by extraction. from a petroleum dioxide.

said volatile hydrocarbon liquid boils above about 122 F. I

7. Composition according to claim 3, in which said solvent boils within' the approximate limits of 2'75 and 365 F.

8. Composition according toclaim 3, in which said solvent boils within the approximate limits or 365and 419? F.

9. Composition according to claim 3', in which said solvent boils within the approximate limits of 419 and 550 F.

10. As a varnish, a composition comprising an organic-substance of the class of gums and resins which are soluble inorganic solvents, dissolvedin an organic vehicle comprising a volatile hy-' drocarbon liquid prepared by destructive-hydro-= genation of a petroleum oil in vapor phase at a temperature above about 900 in excess of 20 atmospheres.'--

11. As a varnish,-a composition comprising, an

organic substance of the class of gumsand resins which are soluble in organic solvents, dissolved a excess of 20 atmospheres. 12. As a baking varnish, prising a drying oil and 4,1 12

and a resin dissolved in: avehiclec 'fpared' by destructive F. and a pressure I in an organic "vehl'c'le con iprlsing; a lhyd oca'rbon liquid having a kauri-butan'ol 'I.value"fabove40, *boiling' within theapproxima' 5 d .419""F.;a-nd prepare b tion ofapetroleum o'iIi'n apo phas ata" m- ;F and pressur ifn perature above about 900 vehicle comprising aj volatile hydrqcarborri-liquid ing a flash point above about80 destructive hydrogenation {of {a vapor phaseat a temperature'iabove'. ab.out;.900f

13. A baking enamel omi rismga d solvent of low volatility, boilifi 'jwith atmospheres.

14. As a lacquer, a'conipdsitio solution of a soluble cellulosefjd organic vehicle, comprisin in excess of 20 atmospheres; 15 As a lacquer, acornp si tiO solution containing asolubl llulose derivative dissolved in an organic vehiclecojnprising a f' tile hydrocarbon liquid-"boiling; withingthe ap- .proximate range of 200 and 275 kaurirbutanol value above 40. andprepared by hav n a rnexcess Lot, 20

a volatileihydrocar-l bon liquid, prepared by destructive, hydrogen-" 1. ation of a petroleum 01. Yapor{pha se.'at'a. temperature above about 900 F. and; a-"pressure i :f

-.-s0 i i ri' 'sing a, v

havinga kauri-butanol'valueaboveawand-have' 7 destructive hydrogenationof a petroleum :oil in vapor phase at a temperature bq about; 900s i F. and a pressure in excess of'2 0Iatmospheres.

16. As a lacquer, a composition. comprising pyroxylin dissolved-in a:' vehicle. comprising aivolatile organic solvent for pyroxylin or th'e'class of aliphatic alcohols, and their fatty. acid esters,

and a, volatile hydrocarbon liquidprepared' by "destructive hydrogenation, of aj petroleum oil in vapor phase at a temperatureabove,about 900 V F. and a pressure in excess of '20: atmospheres.,..f l

. 17..As a lacquer, a composition comprising a:

solution of cellulose ether in an. organic vehicle comprising a volatile hydrocarbon liquid prepared by destructive hydrogenation of a. petroleumoilin. vapor phase at a temperature above about 900" F. and a pressure in excess of 20 atmospheres.

18. As a lacquer, a composition'comprising a soluble cellulose. de'rivativeand blown castor oil dissolved in a vehicle comprising a1 volatile hy-- drocarbon liquid, having a kauri-butanolvalue] above 40, boilingabove about 122 F. and prepared by destructive hydrogenation of a petro+ leum oil in vapor phase at a temperature above about 900? and a pressure in excess of 20 atmospheres' 19. As a paint, a composition comprising apigment admixed with an organic vehicle comprising a solution containing a drying oil and a volatile hydrocarbon liquid prepared by destructive hydrogenation of a petroleum oil. in vapor phase at a temperature above about 900 F. and a pressurein excess of 20 atmospheres.

20. As a paint, a composition comprising a pigment admixed with an organic vehicle, comprising a solution containing a drying oil and a volatile hydrocarbon liquid, boiling within the approximate range ofv 365-"and:550$Fghavingra.

uid, having a kauri-butanol value above 40, and prepared by destructive hydrogenation of a petroleum distillate in vapor phase with a limited proportion of hydrogen under conditions suitable for forming anti-knocking motor fuels.

ROBERT T. HASLAM. 

